Salts of organic dyestuffs



Patented Dec. 6, 1949 UNITED STATES PATENT OFFICE SALTS OF ORGANIC DYESTUFFS John Paige, Albany, N. Y., aalignor to General Anilin e & Film Corporation, New York, N. Y..

a corporation oi Delaware No Drawing. Application May 1, 1946, Serial No. 686,529

It is an object of the preesnt invention to provide coloring matters which may be employed in nitrocellulose lacquer, spirit varnishes and the like.

A further object of the invention is the provision of water insoluble coloring matters which have uses, among others, in coloring varnishes and lacquers and which have good fastness to light.

In accordance with the present invention, an organic dyestufl containing at least one acidic group is reacted with an N-dialkyl polymethyleneolamine wherein the N-dialkyl groups have four carbon atoms, to form a salt which is insoluble in water. The pigment produced is slightly soluble in acetone and readily soluble in methanol, denatured alcohol and in Cellosolve. The compounds of the present invention may be employed directly for coloring nitrocellulose lacquer, varnishes, enamels, or the like, or may be mechanically mixed with a suitable substrata, as for example, aluminum hydroxide, heavy spar, or precipitated barium sulfate, or a mixture thereof may be rubbed on with varnish and printed, or rubbed on with linseed oil and spread or brushed on with an aqueous binding agent, to produce a covering of the desired hue fast to light. They may also be employed for coloring of films, threads, plastic masses as well as surfaces subject to exposure to water. They may be dissolved in various suitable solvents and employed as wood stains, or can be used for the dyestufls containing one or two polyoxygen acidic groups for most purposes, although dyestuffs containing a greater number of acidic groups may be employed. For this purpose, there may be employed, for example, compounds absorbing ultraviolet light, fluorescent compounds, sulfonated phthalocyanines, metallized or not, azo dyes of various kinds containing sulfonic acid groups or carboxylic acid groups, including azo dyes containing arylpyrazolones or sulfoarylpyrazolones as a component, or containing hydroxy or vicinal hydroxy carboxylic acid groups, metallized or not. Examples of such compounds are the combination of diazotized o-aminobenzene sulfonic acid coloring of shellac and various other natural and with 5 oxo-1(o-sulfophenyl)-2-pyrazole-3-carboxylic acid, or diazotized p-aminobenzene sulfonic acid with 1-(2'-chloro-5'-sulfophenyl)- 3-methyl-5-pyrazolone, the chromium complex salt of 2-naphthol-4-sulfonic acid-l-azo-nitrophenylmethyl pyrazolonesulfonamide, diazotized aminobenzenesulfonic acid and 2-benzamido- 5-naphthol-7-sulfonic acid, diazotized p-nitraniline with salicylic acid (C. I. 40), tetrazotized 3,3'-dichlorobenzidine with two moles sodium 2-naphthylamine-3,fi-disulfonic acid (C. I. 436). diazotized m-toluidine with l-benzamido-ll-naphthol-4,5-disulfonic acid, diazotized pphenylazoaniline with 2-naphthol-6,8-disulfonic acid or with 2-naphthol-3,6,8-trisulfonic acid, diazotized aniline with 2-naphtho1-8-sulfonic acid, 6 ureido bis(2 phenylazo-1-naphthol 3 sulfonic acid) and the like. Other classes of suitable compounds include sulfonated anthraquinone coloring matters, such as 1-amino-4-anilino anthraquinone-2-su1fonic acid, 1.4-ditoluino-5.8-dihydroxy anthraquinone disulfonate, sodium-1- amino 4 anilinoanthraquinone 2 sulfonate, 1 (p-acetamidoanilino) -4-aminoanthraquinone- 2-sulfonic acid, 1,4-dihydroxy-5,8-di(p-toluino)- anthraquinone disulfonic acid, 1,5-dihydroxy- 4,8-di(p-tolulno)-anthraquinone disulfonic acid, 1,4-diaminoanthraquinone-2-sulfonic acid, l-hydroxy 4 (p toluino) anthraquinone sulfonic acid, 1,5-di(p-toluino) -anthraquinone disulfonic acid, 6 (sulfo p toluino) anthrapyrimldine, 6-su1fo-toluino-2-anthrapyrimidine, 2-sulfo-phenoxy 1,4 diaminoanthraquinone, polyhydroxyanthraquinone sulfonic acids, such as alizarine sulfonic acid or hexahydroxyanthraquinone-3,7- disulfonic acid, xanthene coloring matters, such 3 as the rhodamines, for example, Violamine B (C. I. 757) acid Violet 4R (C. I. 758), or triarylmethane dyestuffs.

By the term polymethyleneolamine as herein employed is meant the ethylene group or higher homologues thereof having a free hydroxyl group and having also an end amino group. The N-dialkyl poiymethyleneolamines useful in the present invention may be represented by the following formula:

where R represents like or unlike alkyl groups containing 4 carbon atoms, and n is a whole number greater than one. The compounds of the above formula may be prepared in known manner. for example, by acting on monoethanolaminewith a corresponding diaikyl sulfate, such as, forexample, dibutyl sulfate in the presence of an acid binding agent such as caustic soda, or by reacting utea after the addition. A slight tarry-precipitate forms and a spot test on fllter paper shows a very slight red rim. The precipitate is washed with a small amount of water andis then dried. The product is a red powder, insoluble in water, slightly soluble in acetone and readily soluble in methanol, denatured alcohol and in Ceilosolve with a red color.

Similar products are obtained when substituting N-diisobutyl ethanolamine for the N-din-butyi ethanolamine.

Example 2 Using in place oi. the dyestui! in Example 1,

. the yellow dye obtained from diazotized o-sulfanilic acid and N-(o-sulfophenyl)-3-carboxylic acid-5-pyrazolone, there is obtained a yellow powder soluble in methanol, denatured alcohol,

the dibutylamine or diisobutylamine with ethylene oxide.

The reaction with the N dialkyl polyethyleneolamine may be carried out with the acid dyestufi in the form of its free acid, or in the form of the respective metal salt thereof. Where the reaction is carried out in a solvent medium, the pigment solution may be used as such, or the pigment may be precipitated by dilution with water, or by evaporating off the solvent, or in any other suitable manner.

The invention will be described in connection with the following examples:

Example 1 grams of the red dye obtained from diazotized p-amino azo benzene mono sulfonic acid with 2--benzoyl-5-naphthol-7-sulfonic acid are dissolved in about 700 cc. water and heated to about 95 C. A solution containing grams N-di-n-outyl ethanolamine and 20 grams phosphoric acid in about cc. water is added slowly while the temperature is maintained at about C. and stirring continued for about 10 min- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 931,423 Hesse et a1 Aug. 17, 1909 1,836,047 Somerville 1 Dec. 15, 1931 1,836,048 Somerville Dec. 15, 1931 2,022,678 Kritichevsky et al. Dec. 3, 1935 2,095,077 Payne Oct. 5, 1937 2,315,870 Nadler et al. Apr. 6, 1943 

